JPS63139334A - Recording medium - Google Patents

Abstract

PURPOSE:To obtain the titled medium having high sensitivity and preservative stability ad excellent light fastness and capable of giving a clear and high gradient image, without necessity of a light source having high light energy by incorporating a coloring agent and a prescribed sensitive component capable of sensitizing by giving a light energy and an energy capable of converting to heat, to a transferring recording layer. CONSTITUTION:The transferring layer contains the coloring agent and the prescribed sensitive component capable of sensitizing by the light energy and heat or the energy capable of converting to the heat. The sensitive component contains at least a photopolymerization initiator and a monomer having an unsatd. double bond, or its oligomer or its polymer or a mixture thereof. The photopolymerization initiator is composed of at least one kind of the compd. selected from cumalin derivatives and at least one kind of the compd. selected from S-triazines having at least one of trihalomethyl group. A solid image forming material capable of forming the transferring layer is composed of powders (or microcapsules) contg. a binding agent, and is formed to a layer by sticking chemically or physically (for example, electrically) said material on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel recording medium used in recording devices such as printers, copying machines, and facsimiles. In particular, the present invention relates to a recording medium used in a recording method suitable for one-shot color recording.

[Conventional technology]

In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices suitable for each information processing system have also been developed and adopted. One such recording method is the thermal transfer recording method, which uses a lightweight, compact, and noiseless device.
It has excellent operability and maintainability, and has been widely used recently. According to this method, plain paper can be used as the transfer medium.

[Problem that the invention seeks to solve]

However, conventional transfer recording methods are not without drawbacks. This is because in the conventional thermal transfer recording method, the transfer recording performance, that is, the print quality, is greatly affected by the surface smoothness.Good printing is performed on highly smooth transfer media, but on less smooth transfer media. In some cases, the print quality deteriorates significantly. However, even when using paper, which is the most typical transfer medium, highly smooth paper is rather special, and ordinary paper has various degrees of unevenness due to entangled fibers. Therefore, according to the conventional thermal transfer recording method, the edges of the printed image may not be sharp or a portion of the image may be missing, resulting in a reduction in print quality.

In addition, in conventional thermal transfer recording methods, the ink layer is transferred to the transfer medium using only the heat of the thermal head, but the thermal head must be cooled to a predetermined temperature within a limited short period of time. Furthermore, it is logically difficult to increase the amount of heat supplied from the thermal head because of the need to prevent thermal crosstalk between the heat generating segments that make up the thermal head surface. Therefore,
High-speed recording is difficult with conventional thermal transfer recording methods.

In addition, because thermal conduction has a slower response than electricity or light, it is generally difficult to control heat pulses to the extent that halftones can be reproduced when recording with conventional thermal heads. Since the heat-sensitive transfer ink layer does not have a gradation transfer function, it has not been possible to record halftones.

In addition, with conventional thermal transfer recording methods, only one color image can be obtained with one transfer, so to obtain a multicolor image, the colors must be overlapped by repeating the transfer multiple times. was necessary. However, it is very difficult to accurately superimpose images of different colors, and it is difficult to obtain images without color shift. In particular, when focusing on a single pixel, colors are rarely superimposed in a single pixel, and in the end, conventional thermal transfer recording methods result in a collection of pixels with misaligned colors, resulting in multiple colors. It was forming an image. For this reason, clear multicolor images cannot be obtained using conventional thermal transfer recording methods.

In addition, when trying to obtain multicolor images using conventional thermal transfer recording methods, it is necessary to install multiple thermal heads or to make complicated movements such as reverse feeding and stopping of the transfer medium, which requires the entire device. The disadvantages are that the process becomes large and complicated, and the recording speed decreases.

Further, US Pat. No. 4,399,209 discloses a system that uses a color former and a color developer to form a multicolor visible image. U.S. Pat. No. 4,399,209 uses a recording medium in which microcapsules containing a photosensitive composition and a coloring agent are arranged on a substrate, and uses mainly ultraviolet light converted in accordance with a recorded image to The photosensitive composition inside the capsule is cured to form a transferred image, and this transferred image is further superimposed on a recording medium having a color developer layer, and the microcapsule is destroyed by passing it through a nip between a pair of pressure rollers. The present invention also discloses a transfer image forming system that develops an image. A multicolor image is obtained by image-formingly transferring a color former to an image forming sheet, where the color former reacts to form an image.

Further, US Pat. No. 4,416,966 discloses a self-contained color developer in which the color developer is present on the same support surface as the photosensitive microcapsules.
) discloses an image forming system. After exposure, primarily by ultraviolet light converted in accordance with the recorded image, the microcapsules rupture and release the internal phase imagewise when the imaging sheet is passed through a pressure roll. The color former then migrates to a developer, usually provided in a separate layer, where it reacts and forms a color image.

Both of the above two recording methods contain a photoinitiator in a microcapsule, and the photoinitiator has different photosensitive wavelength ranges, and mainly uses ultraviolet light that has been converted to correspond to each photosensitive wavelength range. This hardens the contents inside the microcapsules. However, the common problem with these methods is that the means used for image formation mainly irradiates only ultraviolet light, that is, optical energy, onto the substrate on which the microcapsules are arranged, which makes it difficult to form a transferred latent image on the recording medium. To obtain clear recorded images at high speed,
It was necessary to use a photosensitive material that is highly sensitive to light, or to irradiate it with high-energy light.

However, high-sensitivity recording media that utilize only photoreactions have the fatal drawback of high sensitivity when irradiated with light and poor storage stability near room temperature. Furthermore, in order to obtain high-energy light, the apparatus becomes large, and in order to obtain multicolor recording, the apparatus becomes large and the apparatus cost becomes large, which is not desirable in practice. In addition, since the above method uses only light energy to form an image, it
When outputting an image in response to an external signal, or when converting an image read from a color document into a digital signal using a color image scanner, such as in a color copying machine, and then adding image information to a recording medium, It's inappropriate. That is, when irradiating high-energy light, it is necessary to use short wavelength light, mainly ultraviolet light, and a digitally controllable light source for ultraviolet light is currently not available. For example, as a method for obtaining a digital light source, optical heads such as liquid crystal shutter arrays and LED arrays have been devised, but although these are suitable for miniaturization, liquid crystal molecules deteriorate at wavelengths in the ultraviolet region. UV light cannot be extracted.

Furthermore, since the color development method uses leuco dye, it has the drawback that the stability of recorded images is essentially poor.

Furthermore, in order to facilitate development by applying pressure after exposure, the contents of the microcapsules need to be a photosensitive composition that has a liquid phase at room temperature, resulting in poor storage stability and the resulting images remain unrefined. Because the reactants are destroyed, there is a lingering odor, which is a characteristic that is undesirable for practical purposes.

The present invention provides an image forming method that solves the above conventional problems,
In other words, high-quality transfer images can be formed, high-speed recording is possible,
It is possible to record halftones, and it can be effectively applied to an image forming method that can obtain a clear multicolor image without color shift without making complicated movements on the transfer medium even when obtaining a multicolor transfer image. The main purpose is to provide recording media.

A further object of the present invention is to provide a recording medium that does not require a special color developing layer and can form a clear transferred image on commonly used plain paper with low surface smoothness.

A further object of the present invention is to provide a highly sensitive recording medium that can record digital images with low power without requiring a special digital light source with high optical energy.

Broadly speaking, an object of the present invention is to provide a recording medium with high storage stability and high sensitivity.

A further object of the present invention is to provide a recording medium on which recorded images with excellent light resistance can be obtained.

A further object of the present invention is to provide a recording medium that can produce clear, multicolor recorded images with high gradation using a small and inexpensive device.

A further object of the present invention is to provide a recording medium that can be used in an image forming method with extremely low environmental dependence during latent image formation.

[Means for solving problems]

The above-mentioned object of the present invention is to provide a transfer recording layer in which the physical properties governing the transfer characteristics of the transfer recording layer change by simultaneously applying a plurality of types of energy including light and at least one type of energy corresponding to image recording information. A recording medium having on a support.

The transfer recording layer is formed from an image forming element that is solid at room temperature and includes at least a colorant and a sensitive component that is sensitive to the application of light energy and heat or heat convertible energy, and the sensitive component is a monomer, oligomer, which has at least a photopolymerization initiator and an unsaturated double bond,
It contains a polymer or a mixture thereof, and the photopolymerization initiator consists of at least one compound selected from coumarin derivatives and at least one compound selected from S-triazine having at least one trihalomethyl group. Achieved by recording media.

To perform transfer recording using the recording medium of the present invention, first, multiple types of energy including light are simultaneously applied to the transfer layer in correspondence with the image recording information, thereby improving the transfer characteristics. The physical properties that govern the transfer are changed, and the transferred image formed by the portion where the physical properties have changed is transferred to the transfer recording medium by using, for example, heating and pressure. The physical properties that govern this transfer characteristic are arbitrarily determined depending on the type of recording medium used. For example, in the case of a transfer recording medium that transfers the transferred image in a thermally molten state, it is determined by the melting temperature, softening temperature, or , the glass transition point, etc., and in the case of a transfer recording medium in which the transferred image is transferred in an adhesive state or in a permeable state to the transfer medium, it is the viscosity at the same temperature. Further, the plurality of types of energy used to form a transferred image are arbitrarily determined depending on the type of recording medium used, and, for example, photoelectric f-beam, heat, pressure, etc. are used in appropriate combinations.

A preferred image forming method for forming an image on the recording medium of the present invention will be described. In order to understand this, an example using a recording medium on which a transferred image is formed by light and thermal energy will be explained with reference to FIGS. 1a to 1d.

The time axis of each graph in Figures 1a to 1d (horizontal III
I) correspond to each other. Further, the transfer recording layer contains at least a photopolymerization initiator and a monomer, oligomer, or polymer having an unsaturated double bond, which will be described later, as a sensitive component. FIG. 1a shows the rise in the surface temperature of the heating means and the subsequent temperature drop when the heating means such as a thermal head is driven to develop heat from time 0 to t3. As the temperature of the heating means changes, the transfer recording medium that is in pressure contact with the heating means is
The temperature changes as shown in the figure. That is, the temperature rises with a time delay of tl, reaches the maximum temperature at time t4, which is also delayed from t3, and then decreases thereafter.

Next, the present invention will be explained in detail using the softening temperature.

Let Ts be the softening temperature of the transfer recording layer. The viscosity of the transfer recording layer decreases rapidly in a temperature range of Ts or higher. This situation is shown by white line A in FIG. 1c. After reaching Ts at time t2, the viscosity continues to decrease until time t4 when the maximum temperature is reached, and as the temperature decreases, the viscosity increases again and shows a rapid increase until time t6 when it drops to Ts. In this case, the physical properties of the transfer recording layer are basically unchanged from those before heating, and when heated to a temperature Ts or higher in the next transfer step, the viscosity decreases in the same manner as described above.

Therefore, if the transfer recording layer is brought into pressure contact with the transfer medium and heated to a temperature necessary for transfer, for example, above Ts, the transfer recording layer will be transferred for the same reason as the transfer mechanism of conventional thermal transfer recording. In this case, as shown in Fig. 1d, if light is irradiated at the same time as heating from time t2, the transfer recording layer will soften and, for example, a reaction initiator contained in the transfer recording layer will be activated, and the temperature will reduce the reaction rate. If the temperature rises sufficiently to increase the temperature, the probability that the polymerizable particles will polymerize increases dramatically, so that curing progresses rapidly.

When heating and light irradiation are performed simultaneously in this manner, the transfer recording layer exhibits a behavior as shown by curve B in FIG. 1c. As the reaction progresses, the softening temperature rises and changes from Ts to T's at time t5 when crosslinking ends. This situation is shown in 1d
Shown in the figure. Therefore, when heated in the next transfer step, there will be a difference in properties between the part that has changed to T's and the part that has not changed.

Along with this, the transfer start temperature Ta, which is the temperature at which the transfer recording layer starts transferring, also changes and becomes T'a. Therefore, by heating to Tr that satisfies Ta<Tr<T'a, for example, only the portion where the softening temperature does not rise will be transferred to the transfer medium.

T'5-T at this time depends on the temperature stability accuracy of the transfer process.
s is preferably about 20°C or higher. In particular, the temperature is preferably 40°C or higher. This value is also the same when Ts>T's. In this way, heating or non-heating is controlled according to the image signal,
By simultaneously irradiating light, a transferred image can be formed.

In addition to the softening temperature explained above, the physical properties that govern the transfer characteristics of the transfer recording layer include the melting temperature and the glass transition point, but in any case, the melting temperature, glass transition point, etc. A transferred image is formed in the transfer recording layer by utilizing irreversible changes such as the glass transition point. Further, the softening temperature, melting temperature, and glass transition point vary in almost the same manner, so the above explanation using the softening temperature is also an explanation using the melting temperature and the glass transition point.

Incidentally, the transfer start temperature in the present invention is measured as follows.

A transfer recording layer with a thickness of 6μ coated on a polyethylene terephthalate (PET) film and a surface smoothness (Beck smoothness) used as a transfer medium of 50 to 20 (1 second, high quality paper with a thickness of 0.2 mm are placed facing each other) The transfer recording medium and high-quality paper are sandwiched between the two rolls shown below at a speed of 2.5 mm/s.
It is transported at a speed of ec. The first roll of the two rolls is placed on the transfer recording medium side, is an iron roll with a built-in 300W halogen heater, and has a diameter of 40+ nm.

In addition, the second roll on the high-quality paper side is an iron roll with a diameter of 40+ nm, the surface of which is coated with 0.5 mm thick fluororubber, and the two rolls face each other with a linear pressure of 4 kg/cm. There is. The surface of the first roll is detected by a thermistor, and the halogen heater is controlled to maintain it at a predetermined temperature. Did it pass between two rolls? & After 4 seconds, while keeping the high-quality paper flat, pull the transfer recording medium at an angle of approximately 90° at a speed equal to the transport speed of the roll to separate the transfer recording medium and the high-quality paper, and then peel the transfer recording medium and the high-quality paper to remove the transfer recording layer from the high-quality paper. Observe the presence or absence of transcription. In this way, gradually heat roll (first roll)
While increasing the surface temperature of (heating rate 10℃/M I
N or less) Measure the temperature when the optical density of the transferred image is saturated and find out the transfer start temperature.

Here, physical property changes governing transfer include changes in the glass transition temperature Tg or softening temperature Ts of the recording medium;
However, since the recording medium of the present invention obtains a recorded image in the subsequent transfer step, it is sufficient that the adhesion state or permeability state to the recording medium changes, and the clear above-mentioned Tg.

Adaptation is possible even without a change in Ts or Tm.

In addition, the multiple types of energy used only to form a transferred image include light and heat, or electricity that can be converted into heat;
A combination of energies selected from M sound waves and pressure is preferable in terms of energy efficiency.

Next, the photopolymerization initiator, which is a component of the recording medium of the present invention, will be explained.

It is reported in U.S. Patent No. 4,147,552 and Japanese Patent Publication No. 59-4268 that coumarin derivatives act as photopolymerization initiators.
It is described in Publication No. 4, etc. However, coumarin derivatives alone have a low ability to initiate photopolymerization, and even if light energy and heat or heat-convertible energy are applied to the recording medium as in the present invention, the recording speed is not sufficient.

Therefore, as a result of intensive research, the present inventors found that at least one compound selected from s-triazines having at least one trihalomethyl group (hereinafter S
The present inventors have discovered that the reaction rate of the sensitive component can be increased and the recording speed can be increased by using a combination of compounds selected from the group consisting of -triazine derivatives), thereby leading to the present invention.

Further, when the sensitive component of the recording medium is solid as in the present invention, the reaction rate largely depends on the diffusion rate of the photopolymerization initiator.

Furthermore, when the photopolymerization initiator is a combination of at least one compound selected from coumarin derivatives and at least one compound selected from s-triazine conductors, and is a composite initiator system in which the two have a synergistic effect. Compared to a one-component photopolymerization initiator, the reaction rate depends more on the diffusion rate of the photopolymerization initiator, that is, the probability of association of each component forming the composite initiator system.

Therefore, when recording is performed using both light energy and heat or energy convertible to heat as in the present invention, the diffusion rate of the photopolymerization initiator in the sensitive component increases by applying heat or energy convertible to heat. In this case, when the photopolymerization initiator is in the form of a composite initiator, the reaction rate changes more greatly than when the photopolymerization initiator is a one-component type, and an image with greater contrast is recorded.

In other words, if the photopolymerization initiator is a composite photopolymerization initiator consisting of a combination of a compound selected from coumarin derivatives and a compound selected from S-triazine derivatives, and the synergistic effect is large, only the coumarin derivative can be photopolymerized. The reaction rate of the sensitive component (recording speed of the recording medium) is also higher than when it is used as an initiator, and the reaction rate of the sensitive component is higher than when only light energy is applied to the sensitive component compared to when light energy and heat or energy that can be converted into heat is applied. In this case, as mentioned above, the thermal dependence of the diffusion rate of the photopolymerization initiator is greater for a composite photopolymerization initiator than for a single-component photopolymerization initiator, so that a greater contrast in recording can be achieved.

A typical marine conductor used in the present invention is represented by the following general formula (I) (wherein Q is -CN, or a substituted or unsubstituted heterocyclic ring having 5 to 15 carbon atoms and different atoms constituting the ring). basis,
or Z-R1 (where R1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkoxy group, an alkylthio group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; A substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group having 5 to 15 carbon atoms and different atoms constituting the ring, or a hydroxyl group: and Z is a carbonyl group, a sulfonyl group, a sulphinyl group, or an arylene group. carbonyl group), R2
゜R3, R4 and R5 are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms.
substituted or unsubstituted alkenyloxy group, having 1 to 6 carbon atoms
substituted or unsubstituted alkylthio, dialkylamino group in which each alkyl group has 1 to 4 carbon atoms, hydroxyl group, acyloxy group halogen, nitro group, or 5- or 6-membered heterocyclic group, or 2 or 3 of R2 to R5 and the R
Together with the ring-constituting carbon atoms to which the substituents 2 to R5 are bonded, each fused ring forms a fused ring or fused ring system in which each fused ring is a 5- or 6-membered ring, and R6 is hydrogen and has 1 to 1 carbon atoms. 4 substituted or unsubstituted alkyl groups or 6 to carbon atoms
12 substituted or unsubstituted aryl groups. ) is used. The present invention is not limited to this. Specific examples include 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6
-Methoxycoumarin, 3-benzoyl-8-ethoxycoumarin, 7-medoxy-3-(p-nitrobenzoyl)
Coumarin, 3-benzoylcoumarin, 3-(p-nitrobenzoyl)coumarin, 3-benzoylbenzo[fl coumarin, 3.3'-carbonylbis(7-methoxycoumarin), 3-acetyl-7-methoxycoumarin, 3- Benzoyl-6-bromocoumarin, 3.3'-carponylvistamin, 3-benzoyl-7-dimethylaminocoumarin 3.3'
-Carbonylbis(7-dinithylaminocoumarin), 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-7-methoxycoumarin, 3-acetylbenzo [f] Coumarin, 3-acetyl-7-methoxycoumarin, 3-(1-adamantoyl)-7-methoxycoumarin, 3-benzoyl-7-hydroxycoumarin, 3-hencyyl-6-nitrocoumarin, 3-benzoyl-7 -acetocoumarin, 3-benzoyl-7-ethylaminocoumarin, 7-dimethylamino-3-(4-iodobenzoyl)coumarin, 7-dinithylamino-3-(4-iodobenzoyl)coumarin, 7-dinithylamino-3-(4-sima eilylaminobenzoyl)coumarin, 7-medoxy3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[fl coumarin, 3-(4-ethoxycinnamoyl)-7-medoxycoumarin, 3- (4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-((3-methylbenzothiazol-2-ylidene)
Acetylcocoumarin, 3-((1-methylnaphtho(1,2-d)thiazole-
2-ylidene)acetyl)coumarin, 3.3'-carbonylbis(6-medoxycoumarin), 3.3'-carbonylbis(7-acetoxycoumarin)
, 3.3'-carbonylbis(7-dimethylaminocoumarin).

3.3'-carbonylbis(5,7-diitubroboxy)coumarin, 3.3'-carbonylbis(5,7-di-n-propoxy)coumarin, 3.3'-carbonylbis(5,7-di-n- butoxy)coumarin, 3-cyano-6-medoxycoumarin, 3-cyano-7-medoxycoumarin, 7-medoxy3-phenylsulfonylcoumarin, 7-medoxy3-phenylsulfinylcoumarin, 1,4-biru(7-diethylamino- 3-coumarylcarbonyl)benzene, 7-diethylamino-5,, f'-dimethoxy-3,3
'-Carbonylbiscoumarin, 7-dimethylamino-3-thenoylcoumarin, 7-diethylamino-3-furoylcoumarin, 7-diethylamino-3-thenoylcoumarin, 3-benzoyl-7-(l
-pyrrolidinyl)coumarin, S, 7.6'-1-dimethoxy-3,3'-carbonylbiscoumarin, 5.5.7'-trimethoxy-3,3'-carbonylbiscoumarin, 7-diethylamino-6-methoxy -3,3'-Carbonylbiscoumarin 1. 3-nicotinoyl-7-medoxycoumarin, 3-(2-
3-(7-medoxy-3-damanoyl)-1-methylpyrimidium fluorosulfate, 3-(5,7-jethoxy-3-coumarinoyl)-1- Methyl pyrimidium fluoroborate, N-(7-medoxy-3-coumarinoylmethyl)pyridinium bromide, 9-(7-diethylamino-3-coumarinoyl) -1
,2,4,5,-tetrahydro-311,68,lOH
[f] Benzopyrano(a, 9a, 1-gh) chimerazin-10one, 3-(2'-benzthiazolyl)-
7-dinithylaminocoumarin, 4-methyl-7-dinithylaminocoumarin, 7-dinithylaminocyclobenta[
C] Coumarin, 9-methyljulolidino[9,10-e
]-11) 1-Biran-11-one and the like.

The method for synthesizing the coumarin is described in the above-mentioned US Pat.
47,552 and Japanese Patent Publication No. 59-42684.

In addition, as the S-triazine having at least one trihalomethyl group, the following general formula (I) (wherein X is halogen, R is alkyl, substituted alkyl, aryl, substituted aryl,
A? , alkenyl, substitution? alkenyl group, Q is -CX3.
-Nl2, -NHR', -NR2°, -OR'. (However, R' represents an alkyl group or an aryl group.)
), but the present invention is not limited thereto.

More specific examples include Wakabu et al., Bull, Chem, Soc, Japan.
; Compounds described in 42.2924 (1969), for example, 2-phenyl-4,6-bis(trichloromethyl)-
S-triazine, 2-(p-chlorophenyl)-4,6
-bis(trichloromethyl)-5-triazine, 2-(
p-1lyl)-4,6-bis(trichloromethyl)-3
-triazine, 2- (p-methoxyphenyl)-4゜6-bis(trichloromethyl)-S-triazine, 2-
(2,,4'-dichlorophenyl) -4,6-bis(
trichloromethyl)-8-triazine, 2゜4.6-tris(trichloromethyl)-3-triazine, 2-methyl-4,6-bis(trichloromethyl)-S-triazine, 2-n-nonyl-4, Examples include 6-bis(trichloromethyl)-S-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl>-S-triazine, etc. Also, British Patent No. 138849
Compounds described in Specification No. 2, for example, 2-styryl-4
, 6-bis(trichloromethyl)-S-triazine, 2
-(p-methylstyryl)-4,6-bis(trichloromethyl)-S-1 riazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, -methoxystyryl)-4-amino-6
-trichloromethyl-S-triazine and the like. Also, F.

J, Org, C by 5chaefer et al.
hem: 29, +527 (+964) Compounds described, such as 2-methyl-4,6-bis(tribromomethyl)-3-triazine, 2,4.6-)lis(tribromomethyl)-5-triazine, 2.4.6- Tris(dibromomethyl)-8-triazine, 2-amino-
4-methyl-6-tribromomethyl-S-triazine,
2-methoxy-4-methyl-6-trichloromethyl-S
-Triazines, etc. can be mentioned.

The amount of photoinitiator contained in the sensitive component of the present invention preferably ranges from about 1:5 to about 1:1000 by weight of photoinitiator to compound having unsaturated double bonds. It is possible and more preferably about 1=10 to about 1:
Up to 100.

The weight ratio of the components of the photopolymerization initiator to the coumarin derivative to the S-triazine having at least one trihalomethyl group is preferably in the range from about 30=y to about 1:30, preferably from about 1O:1 to about 1:30. The range is up to IO.

In addition, monomers, oligomers, and polymers having unsaturated double bonds used in the present invention include polyisocyanates (which may be reacted with polyols if necessary), alcohols, and amines having unsaturated double bonds. Urethane acrylates and urethane methacrylates having urethane bonds synthesized by polyaddition reactions of epoxy resins, and epoxy acrylates, polyester acrylates, and spin acrylates synthesized by addition reactions of epoxy resins with acrylic acid or methacrylic acid. , polyether acrylates, etc., but the present invention is not limited thereto.

In addition, as a polymer, it has polyalkyl, polyether, polyester, polyurethane tubes in the main chain,
Examples include those having four major polymerizable and crosslinkable reactive groups in their side chains, such as an acrylic group, a methacrylic group, a cinnamoyl group, a cinnamylidene acetyl group, a furyl acryloyl group, and a cinnamic acid ester. is not limited to this.

It is also desirable that the above-mentioned polymers, oligomers, and polymers be semi-solid or solid at room temperature, but even if they are liquid, they can maintain their semi-solid or solid state by mixing with the binder described below. It doesn't matter if it is. Further, the above-mentioned monomer, oligomer or polymer having an unsaturated double bond and the photopolymerization initiator may be used in combination with a binder.

Any organic polymer may be used as the binder as long as it is compatible with the monomer, oligomer, or polymer having unsaturated double bonds.

As the binder, a conventionally known organic polymer is used. Examples include addition polymers having carboxyl groups in side chains, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, partially esterified maleic acid copolymers, and maleic acid copolymers. In addition, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polymethyl methacrylate, polyacrylic acid,
Polymethacrylic acid, polyacrylic acid, alkyl ester, copolymer of acrylic acid alkyl ester and acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc., polyvinyl chloride, copolymer of vinyl chloride and acrylonitrile, polyvinylidene chloride, Copolymer of vinylidene chloride and acrylonitrile, polyvinyl acetate, copolymer of vinyl acetate and vinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile with butadiene and styrene Copolymers, polyvinyl alkyl ether, polymethyl vinyl ketone, polyethyl vinyl ketone, polyethylene, polypropylene, polystyrene, polyamide, polybutadiene, polyisoprene, polyurethane, polyethylene terephthalate, chlorinated rubber, polychloroprene, polystyrene-butadiene copolymer, and so on. Among the above polymers, polyethylene chloride, polymethyl methacrylate, polyvinyl chloride, vinylidene chloride-acrylonitrile copolymer, polystyrene, styrene-acrylic copolymer, polyvinyl butyral, polyvinyl acetate, vinyl chloride-vinyl acetate There are copolymers, chlorinated rubber, etc. These may be used alone or in a mixture of two or more. The binder is 1wL% to 90w relative to the sensitive component.
L%, preferably 1 wt% to 60 wt%.

Waxes, whether compatible or incompatible, are also used, including vegetable waxes such as candelilla wax, carnauba wax, and rice wax, animal waxes such as beeswax and spermaceti, and mineral waxes such as ceresin and montan wax. Synthetic waxes include petroleum waxes such as polyethylene waxes, paraffin waxes, polyethylene waxes, Sasol waxes, montan wax derivatives, paraffin wax derivatives, hydrogenated castor oil, hydrogenated castor oil conductors, and fatty acids and fatty acid amide esters such as stearic acid. In the present invention, one type or a mixture of two or more types of these waxes may be used.

The colorant is a component contained in order to form a chemically recognizable image, and various pigments and dyes are used as appropriate. Examples of such pigments and dyes include carbon black, yellow lead, molybdenum red, inorganic pigments such as Red Red, Banza Yellow, Benjishi Yellow, Brilliant Carmine 6B, Lake Red C, Permanent Red F5R, Phthalocyanine Blue, and Victoria Blue. Organic pigments such as Lake, Fast Sky Blue, and colorants such as leuco dyes and phthalocyanine dyes can be used.

The amount of coloring agent is 0.000000000000000 with respect to the sensitive component and the binder.
1 to 30 parts by weight is preferred. Furthermore, additives such as thermal polymerization inhibitors and plasticizers may be added to the sensitive component of the present invention, if necessary.

Even if the above-mentioned sensitive component is dissolved in a solvent and coated on a support in a continuous layer, the sensitive component can be formed into a particulate image-forming element, or the particulate image-forming element can be microencapsulated. It may be applied onto a support. The support used in the present invention is selected from film-like materials such as polyethylene terephthalate and polyamide.

The support may be provided with other coating layers, an antihalation layer, an ultraviolet absorbing layer, or a visible light absorbing layer on its surface, if necessary, to facilitate bonding.

Furthermore, in order to prevent a decrease in sensitivity due to oxygen, the composition of the present invention is provided with a removable transparent cover, or a transparent cover is provided on the photosensitive layer as described in Japanese Patent Publication No. 40-17828. A coating layer with low oxygen permeability can be provided.

Further, in the present invention, multicolor image formation is possible by using coumarin or a conventionally known photopolymerization initiator that has different photosensitive wavelength ranges.

Based on the present invention, it is possible to use a recording medium coated in a single layer on a base film, but in order to prevent a decrease in sensitivity due to oxygen inhibition in the atmosphere, a film made of polyethylene, polypropylene, etc. is used as a recording medium. It is also effective to press the film onto the film and peel it off after the transfer image is formed. Furthermore, if the image-forming element is granulated and coated with a high molecular compound having low oxygen permeability, it is possible to prevent a decrease in sensitivity and improve image resolution. Furthermore, multiple types of compositions using coloring materials and coumarins with different photosensitive wavelength regions or conventionally known photopolymerization initiators are microencapsulated and randomly supported on a base film, and each photopolymerization initiator is A recording medium compatible with color recording can be obtained by simultaneously applying a plurality of types of energy including light having wavelengths corresponding to the photosensitive wavelength range, with at least one type of energy corresponding to the image recording information.

When microcapsules are used in the image forming element constituting the transfer recording layer, the above-described material is contained in the core portion. Examples of materials used for the wall material of microcapsules include gelatin, gelatin-gum arabic, sodium alginate, polyvinyl alcohol, ethyl cellulose, nitrocellulose, cellulose-based urea-formalin such as nitrocellulose, resorcinol-formaldehyde, urea-formaldehyde, isocyanate, Isocyanate-polyol, melamine-formaldehyde,
Hydroxypropyl cellulose, polyvinyl chloride, polyvinyl chloride-cellulose, acetate butyrate, polyvinyl acetate, polystyrene, polyethylene, polymethyl methacrylate, polyamide, styrene-acrylonitrile copolymer, vinylisodene chloride-acrylonitrile copolymer, epoxy Resin, polyvinyl formal, vinyl chloride-vinyl acetate copolymer, polyester, polyacrylate, cellulose acetate butyrate, polyvinyl pyrodone, polyvinylidene chloride, nylon, tetron, urethane, polycarbonate, maleic anhydride copolymer , polyethylene terephthalate, etc. are used.

In the transfer recording medium of the present invention, the thickness of the transfer recording layer is 1 to 20
μ is preferable, and 3 to 10 μ is particularly preferable. When the transfer recording layer is composed of image forming elements of microcapsules, the particle size of the macrocapsules is preferably 1 to 20 μm, particularly preferably 3 to 10 μm. Further, the particle size distribution of the microcapsules is preferably ±50% or less, particularly preferably ±20% or less with respect to the number average diameter. The thickness of the wall material of the microcapsule is preferably 0.1 to 2.0μ,
Particularly preferred is 0.1 to 0.5μ.

Any conventionally known method can be applied as the microencapsulation method, such as simple coacervation method,
Complex coacervation method, interfacial polymerization method, 1
The n-situ polymerization method, interfacial precipitation method, phase separation method, spray drying method, air suspension coating method, mechanochemical method, etc. are used.

The microcapsule image forming element is bound to the substrate using a coating binder such as polyvinyl alcohol (PVA) or epoxy adhesive. The thickness of the coating binder is preferably 0.1 to 1 μm.

In the recording medium of the present invention, radical reactions in the transfer recording layer may be suppressed due to oxygen in the air. In order to prevent this, it is preferable to apply, for example, an aqueous polyvinyl alcohol solution to which a small amount of a surfactant is added as an oxygen-preventing layer on the transfer recording layer. This oxygen prevention layer is removed by washing with water after the transfer image is formed. In addition, in the case of a microencapsulated element, the wall material can have a function as an oxygen prevention layer.

The recording medium of the present invention can be manufactured, for example, as follows.

The recording medium of the present invention is prepared by melt-mixing components such as a sensitive component, a stabilizer, a coloring agent, and applying the mixture onto a substrate using an applicator or the like. In addition, when the transfer recording layer is constituted by an image forming element, the above-mentioned components are made into minute image forming elements by spray drying method etc. for each color, and then each color image forming element is formed with a binder such as a polyester resin. After thoroughly mixing the body in a solvent such as methyl ethyl ketone or ethylene glycol diacetate, solvent vent coating is performed on a film such as polyimide, and the solvent is removed by drying at 80° C. for 3 minutes to form the desired recording medium 4. You can get a body.

When the image-forming element is composed of microcapsules, the image-forming element of microcapsules is manufactured, for example, by a method detailed in the Examples below,
It is coated on a substrate by a solvent coating method in the same manner as in the case of image forming elements on particles.

Further, the particulate element may be electrostatically attached to a support, and in that case, the particulate element or the support or both are corona charged or fJ triboelectrically charged.

The method of physically or chemically supporting the image forming element on the support as referred to in the present invention 22 includes the above-mentioned solvent coating method, electrostatic adhesion method, etc. As a chemical method, there is a method in which the image forming element and the support are provided with respective functional groups on the surfaces in contact with each other and chemically bonded to each other.

Examples of the support include polyester, polycarbonate, triacetylcellulose, nylon, polyimide, polyethylene terephthalate, and metals such as aluminum, and these may be in the form of a film, plate, drum, or sphere.

〔Example〕

The present invention will be explained below using examples.

Example 1 The components shown in Table 1 were dissolved in dichloromethane solvent,
It was coated on a polyethylene terephthalate film having a thickness of 6 µj with a thickness of 4 scales. Apply a polyvinyl alcohol (1200) aqueous solution to the crotch to prevent oxygen.
(film thickness top) was formed and used as a sample.

Next, the sample prepared by the above method was wound into a roll and incorporated into the apparatus shown in FIG. 2.

The thermal head 4 is a line type of 8-4 size with 8 dots/111111, and a row of heat generating elements is arranged at the edge part, and is arranged so that the base material side of the recording medium 1 is in contact with the heat generating elements. The tension of the recording medium 1 was made to press against the heating element. A chemical lamp (emission peak: 450 mm, manufactured by Toshiba Corporation, FLIOA70 [1) 3 was placed at an opposing location.

Next, the heat generation of the thermal head is controlled according to the image signal.

In this embodiment, since the transfer recording layer is treated with light and heat applied to raise the glass transition point and the transfer start temperature, negative recording is performed. That is, the thermal head is controlled such that it does not conduct electricity when a mark signal (black) is present, but conducts current when it is not a mark signal (white) to generate heat.

The energizing energy during this heat generation is 0.8w/dotX3.
It was 0m5ec. In this way, the thermal head is controlled and driven according to the image signal in the manner described above while uniformizing the light irradiation with the chemical lamp, and the 10 m5 ec/1 in.
The transfer recording medium was conveyed by a stepping motor and a drive rubber roll in synchronization with a repetition period of .

Next, the polyvinyl alcohol film was removed, and as shown in FIG.
It was transported by sandwiching it between the two. The beat roll 8 was an aluminum roll having a 300 W heater 7 inside and whose surface was coated with silicone rubber having a thickness of 2 mff1, and the heater was controlled so as to maintain the surface at an arbitrary temperature in the range of 50 to 150°C. The pinch roll 9 was a silicone rubber roll with a hardness of 50° measured by a JIS rubber hardness meter, and the pressure was 1 to 1.5 Kg/Cn12.

After conveying the plain paper over the transfer recording layer at a heat roll temperature in the range of 90 to 150°C, when the base film was peeled off, a high-quality image with good fixability was formed.

Comparative Example 1) A sample was prepared in the same manner as in Example 1) using the materials shown in Table 1 except that the S-triazine derivative was removed, and a drawing experiment was conducted. The electrical energy applied to the thermal head was 0.9 W.
/ doLX 80m5ec, repeat 150m5e
c/1ine, images were formed at 90-100°C with a heat roll.

Comparative Example 2) A sample was prepared in the same manner as in Example 1) with the composition shown in Table 1 except that the coumarin derivative was removed, and a printing experiment was conducted. Even if the amount of energy was changed, no image that could be recognized as an image could be obtained.

As is clear from Comparative Examples 1) and 2), coumarin derivatives and S-
It was found that when a triazine derivative is used in combination, images with high sensitivity and good contrast can be obtained.

Example 2) A drawing experiment was conducted by preparing a sample with the components shown in Table 2 in the same manner as in Example 1, and the current energy of the thermal head was 0.9 w/dot x 7.0 m5ec, repeated 16 times.
+n5ec/mne, beat roll temperature 90-130℃
As in Example 1), a high quality image with good fixability could be formed. However, the light source 3 is a chemical lamp (Toshiba F
LIO^70BL/33TI5) was used.

Next, an example will be shown in which a multicolor image was created using the recording medium of the present invention.

Example 3) As shown in FIG. 4, the transfer recording layer 1b has a core lc.

A microcapsule-shaped image forming element was formed by using the material having the composition shown in Tables 3 and 4 as 1d by the method shown below.

That is, 10 g of the ingredients shown in Tables 3 and 4 were first mixed with 20 parts by weight of methylene chloride, and then mixed with 200 ml of water in which 1 g of gelatin was dissolved and a surfactant with an HLB value of at least 10, such as a cation or nonion. 8,000~IQ, OQOr using a homomixer under heating at 60℃
Stir at pm to emulsify and obtain oil droplets with an average particle size of 26 μm.

Table 3 Table 4 Stirring was continued at 60° C. for 30 minutes, and methylene chloride was distilled off to reduce the average particle size to 10 scales. Add 20 parts of water in which 1 g of gum arabic has been dissolved, cool slowly and then add HH40H (ammonia) water to adjust the pH.
1 or more to obtain a microcapsule slurry, and slowly add 1.0 ml of a 20% glutaraldehyde aqueous solution to harden the capsule walls.

After that, solid-liquid separation was carried out using a Nutsche filter, and 35
C. for 10 hours to obtain a microcapsule-shaped image forming element.

This image forming element has cores lc and l shown in Tables 3 and 4.
d is a microcapsule covered with a shell 1e, which is formed to have a particle size of 7 to 15 μs and an average particle size of lOμ.

The image forming element formed as described above was coated with 5% PVA.
A transfer recording layer 1b is formed by adhering onto a support la made of a 6-thick polyethylene terephthalate film using an adhesive 1f made of an aqueous solution and several drops of a surfactant per 100 cc, thereby forming a recording medium 1. Configure.

The coumarin derivative in the image forming element shown in Table 3 absorbs light in the band of graph C in the light absorption characteristics shown in FIG. 5, and becomes magenta in color during image formation. The coumarin derivative absorbs light in the band of graph D in the light absorption characteristics shown in FIG. 5, and becomes blue when forming an image. Next, the transfer recording layer 1b was wound into a roll and incorporated into the apparatus shown in FIG.

However, the light source indicated by 3 here is a lamp E with an emission peak of 450 mm corresponding to the coumarin derivative exhibiting the above-mentioned absorption characteristics.
(Toshiba Corporation FL10A70B) and luminescence peak 352
mm lamp F (Toshiba Corporation FLIOA70BL /
33TI5) are placed. When the transfer recording layer 1b is exposed to light of a predetermined wavelength and heat, the softening point temperature increases,
6th because it has the property of not being transferred to recording paper.
As shown in the timing chart in the figure, when recording magenta, the heating element 4 corresponding to magenta of the image signal is not energized in the heating element array of the thermal head, and the white (white) of the image signal is not energized.
25m5ec in the area corresponding to the recording medium (white)
At the same time, the lamp E was irradiated uniformly for an irradiation time of 30 m5ec.

Next, for blue recording, after 25 m5 ec has passed after the end of the irradiation, that is, 50 m5 ec after the energization time, the image signal is sent without energizing the heating element corresponding to the blue color of the image signal in the heating element array of the thermal head. A current of 35 m5 ec is applied to the portion corresponding to white, and at the same time, lamp B is uniformly irradiated for an irradiation time of 45 m5 ec. In the manner described above, the thermal head is controlled according to the blue, magenta, and white image signals to form a negative image on the transfer recording layer 1b, and the transfer length is 100 m.
The transfer recording medium 1 is conveyed synchronously at a repeating period of 5 ec/line.

Next, as in Example 1), plain paper was layered on the transfer recording layer,
By applying pressure and heating, a two-color transfer image of blue and magenta can be transferred onto plain paper.

As described above, two-color recording is performed in one shot.

Example 4) The coumarin derivatives in Table 3 of Example 3 were replaced with 7-ethylamino-3-thienoylcoumarin, and the coumarin derivatives in Table 4 were replaced with Irgacure 184 (Ciba Geigy) and S
- Triazine was replaced with ethyl-P-dimethylaminobenzoate (i.e., in Table 3, the photoinitiator disclosed in the present invention was used, and in Table 4, a conventionally known photoinitiator was used), and Example 3. Microencapsulated in the same manner, 7
- On the side containing diethylamino-3 thienoylcoumarin, lamp E' (Matsushita FLR16A
70-BA42/33T16), Irgacure 18
On the side including 4, there is a lamp F' with an emission peak of 313+am.
(Toshiba FLI 0A70E31/33T15) and in the same manner as in Example 3, two-color recording is performed in one shot by applying light and heat as shown in the timing chart of FIG.

〔Effect of the invention〕

As explained above, if the recording medium of the present invention is used, the formation of a latent image corresponding to an image and the transfer recording are performed in separate processes, so a high-quality image can be formed and halftone recording is possible. Furthermore, multicolor recorded images can be easily and inexpensively formed.Furthermore, when the transfer recording layer is composed of granular image forming elements, the individual solid image forming elements adhere to the recording material. Because transfer recording is performed, a clear, fog-free recorded image can be obtained even on commonly used plain paper with low surface smoothness.Furthermore, it uses light and heat, or energy that can be converted into heat, to form a latent image. Furthermore, the recording medium of the present invention is one in which a latent image is formed only when light and heat or energy that can be converted into heat is simultaneously applied. Therefore, it is possible to simultaneously satisfy both high-sensitivity recording and storage stability.

[Brief explanation of the drawing]

Figures 1a to 1d are diagrams of the principle of transfer recording using the recording medium of the present invention, and Figures 2 and 3 are schematic diagrams of an apparatus for performing transfer recording using the recording medium of the present invention. , FIG. 4 is a configuration diagram of the transfer recording medium, FIG. 5 is an explanatory diagram showing the light absorption characteristics of the coumarin derivative in the transfer medium, and FIGS. 6 and 7 are timing charts for applying heat and light. It is. DESCRIPTION OF SYMBOLS 1...Recording medium, 1a...Support, lb-...Transfer recording layer, fc, 1d''-: fa, 1e...is shell (wall material), 1f-...adhesive , 2... Supply roll, 3... Lamp, 4... Thermal head, 5...
Control circuit, 7... Heater, 8... Beat roller, 9... Pinch roller-110-... Plain paper, 11.
... Winding roll, 12... Recorded image.

Claims (4)

[Claims] (1) By simultaneously applying multiple types of energy, including light, at least one type of energy corresponding to image recording information, a transfer recording layer whose physical properties governing its transfer characteristics change can be formed on a support. an image-forming element that is solid at room temperature, the transfer recording layer comprising at least a colorant and a sensitive component that is sensitive to the application of light energy and heat or heat-convertible energy; The sensitive component contains at least a photopolymerization initiator and a monomer, oligomer, polymer, or a mixture thereof having an unsaturated double bond, and the photopolymerization initiator is at least one selected from coumarin derivatives. and at least one trihalomethyl group
- at least one compound selected from triazine. (2) The recording medium according to claim 1, wherein the image forming element contains a binder. (3) Claim 1 or 2, wherein the image forming element is in the form of particles and is physically or chemically supported on the support to form a layer. recording medium. (4) The recording medium according to claim 3, wherein the image forming element is covered and encapsulated with a wall material.